CN105294995B - Biological based epoxy curing agent and preparation method thereof - Google Patents
Biological based epoxy curing agent and preparation method thereof Download PDFInfo
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- CN105294995B CN105294995B CN201510873058.1A CN201510873058A CN105294995B CN 105294995 B CN105294995 B CN 105294995B CN 201510873058 A CN201510873058 A CN 201510873058A CN 105294995 B CN105294995 B CN 105294995B
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Abstract
The invention discloses a kind of novel epoxy curing agent, which is：R therein1For unsaturated acids anhydride group, R2For polyacid or anhydride group.The invention also discloses the preparation methods of the curing agent, prepare the polymer of double carboxy blockings first using biology base lactic acid monomer as initial feed, multiple anhydride molecules are then grafted on side chain；The both-end carboxyl of obtained curing agent acts synergistically with anhydride group in the epoxy resin cure stage, can improve curing efficiency, shortens hardening time；The presence of the flexible chain structure of curing agent mid-molecule point simultaneously also functions to the effect of certain toughening.In addition, the curing agent synthesis technology of the present invention is simple, less toxic, non-stimulated, environmentally safe, and there is preferable compatibility with epoxy resin, cured product good mechanical performance, flexibility are preferable, dosage is few, be suitable for medium temperature condition under cure, there is larger market application and development value in epoxy resin fasting plastics, laminate and other field of compound material.
Description
Technical field
The present invention relates to epoxy curing agent and its technology of preparing, specifically a kind of new bio base epoxy
Curing agent and its corresponding preparation method.
Background technology
Epoxy resin refers to contain active epoxide group in strand, and can be crosslinked with a plurality of types of curing agent
It reacts and forms insoluble, insoluble a kind of high molecular material with three-dimensional net structure build high polymer；Due to its adhesion strength
By force, good mechanical performance, stable chemical performance, resistant to chemical etching, electrical insulating property is good and shrinking percentage is low and it is convenient to cure and
It is widely used in the multiple fields such as adhesive, fiberglass prepreg and chemical machinery product, automotive interior part.In recent years with
The variation of domestic and international market demand, people are to the focus of epoxy resin product gradually to high-performance, low cost, green ring
Protect, pollution-free, raw material is renewable etc. starts to change, this requires research staff not only will be from the structure of epoxy resin in itself
Set out selection or modified resin matrix, while also to research and develop novel curing technology to meet the needs of more areas.From
For production application angle, a kind of exploitation of novel epoxy hardener, other than meeting resin cured matter performance indicator, simultaneously
To consider the factors such as raw material sources, curing process, environmental protection, the market demand and financial cost.
Acid anhydride type curing agent is a kind of using more extensive curing agent in epoxy curing agent, is not only had low
The features such as volatility, low toxicity, non-stimulated, and cured product shrinking percentage is relatively low, excellent heat resistance, higher mechanical strength, still
Solidification process is slow, needs under hot conditions to cure, and cure cycle is longer mostly, gained cured product is often more crisp, flexible
Property is poor, and high performance curing agent cost is higher, is unfavorable for mass producing.
Invention content
The object of the present invention is to provide a kind of better epoxy curing agents of performance, are consolidated with solving existing Common curing agents
Change the problem of temperature is high, curing degree is undesirable, cured product poor mechanical property.
The object of the present invention is achieved like this：
A kind of new bio based epoxy curing agent, structural formula are：
Wherein m value ranges are the positive integer between 3~100, R1For not
Saturation anhydride group, R2For polyacid or anhydride group.
New bio based epoxy curing agent of the present invention, the R1For：
The R2For：
The present invention also provides the preparation methods of the biological based epoxy curing agent, include the following steps：
(1) after lactic acid being carried out predrainage processing, under catalyst existence condition, polymerisation is carried out, treats that reaction finishes,
Cooled to room temperature obtains prepolymer；
(2) under nitrogen protective condition, polyacid and/or acid anhydrides is added in after the prepolymer heating melting, is deposited in catalyst
Controlling reaction temperature and pressure depressurize 2~3h of polymerisation between 145~170 DEG C, 0.01~0.1MPa respectively under conditions,
Obtain the intermediate polymer of double carboxy blockings；
(3) under nitrogen protective condition, by the acetone soln of intermediate polymer and 60~95 DEG C of constant temperature in advance reflux 20~
Then 40min adds in the acetone soln of unsaturated acid anhydride by several times, atmospheric pressure reflux reacts 3~10h under the conditions of 80~120 DEG C, obtains slightly
Product；Wherein, initiator is also added in the acetone soln of the unsaturated acid anhydride；
(4) gained crude product is dissolved in organic solvent, and the methanol-water mixture stirring for then adding in volume ratio 2: 1 carries out
Precipitation process filters later, recycles filter residue, washs and dry, obtains pale brown color substance, as described biology base epoxy resin cure
Agent.
The preparation method of biology based epoxy curing agent of the present invention, in step (2), polyacid and/or acid anhydrides
Inventory is the 0.5~3% of the lactic acid inventory.
The preparation method of biology based epoxy curing agent of the present invention, in step (3), the acetone of intermediate polymer
In solution, intermediate polymer is 25~40g: 100~200mL with acetone amount ratio；The acetone soln of the unsaturated acid anhydride
In, unsaturated acid anhydride and initiator gross mass and acetone amount ratio are 1.25~6g: 10~25mL.
Preferably, the preparation method of biological based epoxy curing agent of the present invention, in step (3), unsaturated acid anhydride
Inventory is the 5~20% of the intermediate polymer inventory.It is further preferred that biology base epoxy of the present invention
The preparation method of curing agent, in step (3), the initiator amount is the 0.05~1% of the intermediate polymer inventory,
Preferably 0.1~1%.
The preparation method of biology based epoxy curing agent of the present invention, in step (2), the polyacid is fourth two
In acid, adipic acid, azelaic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid, maleic acid, itaconic acid
Any one or two or more arbitrary arbitrary proportion mixture；The acid anhydrides for acetic anhydride, succinic anhydride, oneself two
Acid anhydrides, phthalic anhydride, maleic anhydride, itaconic anhydride, methyl tetrahydro phthalic anhydride, pyromellitic acid anhydride, nadic acid
Appoint in acid anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, cyclobutanetetracarboxylic dianhydride and allyl succinic anhydride
It anticipates the mixture of two or more a kind of or arbitrary arbitrary proportion.
The preparation method of biology based epoxy curing agent of the present invention, in step (3), the unsaturated acid anhydride is four
Hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride, 3- methyl tetrahydro phthalic anhydrides, 4- methyl tetrahydro phthalic anhydrides, maleic anhydride, 2- citraconic acids
Acid anhydride, 2,3- dimethyl maleic anhydrides, carbic anhydride, methylnadic anhydride, itaconic anhydride, maleopimaric anhydride, poly- isobutyl
In enetutanedioic acid anhydride, allyl succinic anhydride and 2,3- dichloromaleic anhydrides any one or it is arbitrary two or more
The mixture of arbitrary proportion.
In the preparation method of biology based epoxy curing agent of the present invention, step (1) is specifically：By lactic acid 110
4~6h of decompression dehydration or lactic acid is pre-processed into more than 48h through molecular sieve under the conditions of~130 DEG C, obtain the lactic acid of predrainage；It will
The lactic acid of the predrainage is gradually heating to 160 DEG C in 0.01MPa pressure conditions, then adds in catalyst, keep 160 DEG C,
0.01MPa conditions carry out 6~10h of polymerisation, treat that reaction finishing, cooled to room temperature is to get to prepolymer.
The preparation method of biology based epoxy curing agent of the present invention, in step (1) and step (2), the catalysis
Agent is zinc class catalyst or tin catalyst；The zinc class catalyst is zinc lactate or ZnO, and the tin catalyst is SnCl2、
Sn(Oct)2, dibutyl tin laurate, dibutyltin diacetate or two (dodecyl sulphur) dibutyl tins.
Preferably, the preparation method of biological based epoxy curing agent of the present invention, in step (1), the use of catalyst
Measure the 0.15-0.5wt% for the lactic acid inventory；In step (2), the dosage of catalyst is the prepolymer and described polynary
The 0.15-0.5wt% of acid and/or acid anhydrides total amount of feeding.
The preparation method of biology based epoxy curing agent of the present invention, in step (2), reaction temperature is preferably controlled in
150~165 DEG C.
The preparation method of biology based epoxy curing agent of the present invention, in step (3), initiator is benzoyl peroxide first
Acyl (BPO), peroxidized t-butyl perbenzoate (TBPB), cumyl peroxide (vulcanizing agent DCP), 2,5- dimethyl -2,5- two
The mixture of any one or two or more arbitrary arbitrary proportion in (t-butylperoxy) hexane.
Further, the preparation method of biological based epoxy curing agent of the present invention, in step (3), the insatiable hunger
With, also added with antioxidant, the antioxidant is 2,5- ditert-butylhydro quinones in the acetone soln of acid anhydrides, 4,4 '-sulphur
Dai Shuan (6- tertiary butyl -3- methylphenols) or three-(3,5- di-t-butyl -4- hydroxybenzyls) chlorinated isocyanurates.
Specifically, the preparation method of biology based epoxy curing agent of the present invention, described organic molten in step (4)
Agent is THF, chloroform, dichloromethane or N,N-dimethylformamide.
In the present invention, maleopimaric anhydride can refer to " research [J] of the maleopimaric anhydride new synthetic methods such as Meng Fanjun
Journal of Shandong university (Edition), 2007,42 (3) " or " Lin Guifu, the synthesis and its curing of the small peace maleopimaric anhydrides of Nie
Response characteristic study [J] thermosetting resins, 2010,04 (04) 1-4.) " disclosed in method be prepared；
Polyisobutenyl succinic anhydride model T2007A or T2007B；
The structure of methylnadic anhydride is
The preparation of the curing agent of the present invention is using biology base lactic acid monomer as initial feed, and raw material is cheap and easy to get and is produced into
This is relatively low；Under the premise of existing for the double carboxy blockings of polymer flexibility chain and initiator, cause (tertiary carbon on polymer flexibility chain
Atom) a certain amount of active site is produced, therefore multiple anhydride molecules can be grafted on side chain；Pair of obtained curing agent
End carboxyl acts synergistically with anhydride group in the epoxy resin cure stage, can improve curing efficiency, shortens hardening time；Simultaneously
The presence of the flexible chain structure of curing agent mid-molecule point also functions to the effect of certain toughening.In addition, the curing agent of the present invention closes
There is preferable compatibility, cured product power into simple for process, less toxic, non-stimulated, environmentally safe, and with epoxy resin
Learn function admirable, flexibility is preferable, dosage is few, be suitable for medium temperature condition under cure, in epoxy resin fasting plastics, laminate and other multiple
Condensation material field has larger market application and development value.
Description of the drawings
Fig. 1 is the infrared spectrum of the biology base epoxy hardener prepared by embodiment 1.
Fig. 2 is the infrared spectrum of the epoxy resin cured product prepared by experimental example 1.
Specific embodiment
Embodiment 1
(1) 250g lactic acid monomers are taken in the three-necked flask of 500mL, control reaction system pressure is under the conditions of 0.01 MPa
110 DEG C of vacuum distillation 6h remove Free water；Then it keeps 0.01MPa pressure conditions constant, is gradually heating to 160 DEG C, adds in
0.38g catalyst zinc lactate the 0.15% of lactic acid monomer quality (addition be) can obtain after 160 DEG C of polymerisation 10h pre-
Polymers；
(2) in N2Under existence condition, 120g prepolymers are weighed in reaction kettle, and being gradually heating to 120 DEG C makes it completely molten
Melt, (addition is prepolymer for addition 3.6g 1, 4- succinic acids (addition is the 3% of pre-polymerization amount of substance) and 0.618 g zinc lactates
With the 0.5% of 1, 4- succinic acid gross mass) it is mixed evenly, and be gradually heating to 170 DEG C, control system pressure is
0.085MPa, reaction 2h obtain the intermediate polymer of carboxy blocking；
(3) in logical N2Under conditions of, 70g intermediate polymers is taken to be dissolved in the acetone of 200mL, are gradually heating to 85 DEG C,
Constant temperature flows back 30min in advance；Taking 10.5g maleic anhydrides and 0.322g peroxidized t-butyl perbenzoates, (addition is respectively poly-
It closes the 15% of amount of substance and 0.4%) is dissolved in 25mL acetone, add in the intermediate polymer solution through flowing back in advance and stir several times
Mix uniformly mixed, 100 DEG C of back flow reaction 8h can obtain crude product；
(4) 35g crude products are dissolved in 100mL THF, then add in 400mL methanol-water solutions (V:V=2:1) it stirs
Precipitation process is carried out, is then filtered, after gained filter cake is rinsed 2-3 times with deionized water, is placed in 55 DEG C of dryings in vacuum drying chamber
48h, it is biology base epoxy hardener to obtain pale brown color substance.
The infrared spectrum of biology base epoxy hardener prepared by the present embodiment is detected, as a result as shown in Fig. 1,
It can be seen that 2990cm in the spectral line of biology base curing agent-1And 2939cm-1Respectively CH3With the stretching vibration absworption peak of CH,
1452cm-1And 1375cm-1Respectively CH and CH3Bending vibration absorption peak, 1739cm-1For the stretching vibration absworption peak of C=O,
Simultaneously in 1180cm-1And 1079cm-1There is the characteristic absorption peak of C-O-C in place, it was demonstrated that the presence of ester bond, and
3500cm-1The characteristic absorption peak of OH is nearby hardly visible, this is because the terminal hydroxy group on lactic acid oligomer molecular backbone occurs
Esterification, is replaced, thus deducibility forms the formation of end carboxyl polymer by carboxyl；From the spectrogram of maleic anhydride
It is upper to can see 1857cm-1And 1764cm-1There is the characteristic absorption peak of acid anhydrides, 3125cm in place-1Nearby occur=C-H
Stretching vibration absworption peak, 1631cm-1Characteristic absorption peak for C=C；Compared to the spectrogram of maleic anhydride, biology base curing
In 1841cm in the spectrogram of agent-1(the asymmetric stretching vibration of C=O) and 1739cm-1(the symmetrical stretching vibration peak of C=O and end
Carboxyl polylactic acid is overlapped and is strengthened) equally there is the characteristic absorption peak of acid anhydrides, and move to lower wave number direction, and=C-H
Stretching vibration absworption peak completely disappear, 1637cm-1The characteristic absorption peak of place C=C significantly weakens, this is because C=C is causing
Under the action of agent with the-CH (CH on polymer molecular chain3) addition reaction has occurred, C=C double bonds become C -- C single bond, acid anhydrides
It has been grafted on the side chain of polymer, the structure that thus can determine curing agent is：
GPC detections are carried out to the molecular weight of the curing agent prepared by embodiment, as a result show invention curing agent it is opposite
Molecular weight is about 400-5000g/mol, and m value ranges thus can be speculated substantially in 3-100.
Embodiment 2
(1) 250g lactic acid monomers are taken in the three-necked flask of 500mL, control reaction system pressure is under the conditions of 0.01MPa
120 DEG C of vacuum distillation 4h remove Free water；Then it keeps 0.01MPa pressure conditions constant, is gradually heating to 160 DEG C, adds in
1.25g catalyst SnCl2The 0.5% of lactic acid monomer quality (addition be), it is i.e. available after 160 DEG C of heat preservation polymerisation 6h
Prepolymer；
(2) in logical N2Under conditions of, 120g prepolymers are weighed in reaction kettle, and being gradually heating to 120 DEG C makes it completely molten
Melt, add in 1.8g phthalic anhydrides (addition is the 1.5% of pre-polymerization amount of substance) and 0.365 g catalyst SnCl2 (additions
0.3% for prepolymer and acid anhydrides gross mass) it is mixed evenly, and be gradually heating to 160 DEG C, control system pressure is
0.085MPa, reaction 2.5h obtain the intermediate polymer of carboxy blocking；
(3) in logical N2Under conditions of, 65g intermediate polymers is taken to be dissolved in the acetone of 150mL, are gradually heating to 85 DEG C,
Constant temperature flows back 30min in advance；Taking 3.25g methyl tetrahydro phthalic anhydrides and 0.26g benzoyl peroxides, (addition is respectively among polymer
Weight 5% and 0.4%) be dissolved in 25mL acetone, add in the intermediate polymer solution through flowing back in advance and stir several times
It is uniformly mixed, 120 DEG C of back flow reaction 3h can obtain crude product；
(4) 40g crude products are dissolved in 120mL THF, then add in 500mL methanol-water solutions (V:V=2:1) it stirs
Precipitation process is carried out, is then filtered, after gained filter cake is rinsed 2-3 times with deionized water, is placed in 55 DEG C of dryings in vacuum drying chamber
48h, it is biology base epoxy hardener to obtain pale brown color substance.
Infrared spectrum detection can determine that the structure of the curing agent prepared by the present embodiment is：
Embodiment 3
(1) 250g lactic acid monomers are taken in the three-necked flask of 500mL, control reaction system pressure is under the conditions of 0.01 MPa
130 DEG C of vacuum distillation 5h remove Free water；Then it keeps 0.01MPa pressure conditions constant, is gradually heating to 160 DEG C, adds in
Two fourth of 0.75g catalyst dibutyltins cinnamic acid, two tin the 0.3% of lactic acid monomer quality (addition be), it is i.e. available after polymerisation 8h
Prepolymer；
(2) in N2Under existence condition, 120g prepolymers are weighed in reaction kettle, and being gradually heating to 120 DEG C makes it completely molten
Melt, add in 3g maleic anhydrides (addition is the 2.5% of pre-polymerization amount of substance) and 0.1845 g dibutyl tin laurates (add
Enter 0.15% that amount is prepolymer and acid anhydrides gross mass) it is mixed evenly, and be gradually heating to 145 DEG C, control system pressure
The intermediate polymer of carboxy blocking is obtained for 0.085MPa, reaction 3h；
(3) in logical N2Under conditions of, 45g intermediate polymers is taken to be dissolved in the acetone soln of 150mL, are gradually heating to 85
DEG C, constant temperature flows back 30min in advance；Taking 9g carbic anhydrides and two different phenylpropyl alcohol of 0.27g peroxidating, (addition is respectively polymer quality
20% and 0.5%) be dissolved in 25mL acetone, add in several times in the intermediate polymer solution through flowing back in advance be stirred
Even, 80 DEG C of back flow reaction 10h can obtain crude product；
(4) 35g crude products are dissolved in 150mL THF, then add in 500mL methanol-water solutions (V:V=2:1) it stirs
Precipitation process is carried out, gained filter cake is rinsed 2-3 times with deionized water after filtering, is subsequently placed in 55 DEG C of dryings in vacuum drying chamber
48h obtains pale brown color substance, as biology base epoxy hardener.
Infrared spectrum detection can determine that the structure of the curing agent prepared by the present embodiment is：
Embodiment 4
(1) 250g lactic acid monomers are taken in the three-necked flask of 500mL, control reaction system pressure is under the conditions of 0.01 MPa
130 DEG C of vacuum distillation 4h remove Free water；Then it keeps 0.01MPa pressure conditions constant, is gradually heating to 160 DEG C, adds in
0.75g catalyst SnCl2The 0.3% of lactic acid monomer quality (addition be) can obtain prepolymer after polymerisation 8h；
(2) in N2Under existence condition, 100g prepolymers are weighed in reaction kettle, and being gradually heating to 120 DEG C makes it completely molten
Melt, (addition is pre- for addition 3g succinic anhydrides (addition is the 3% of pre-polymerization amount of substance) and 0.206g dibutyl tin laurates
The 0.20% of polymers and acid anhydrides gross mass) it is mixed evenly, and be gradually heating to 145 DEG C, control system pressure is
0.085MPa, reaction 3h obtain the intermediate polymer of carboxy blocking；
(3) in logical N2Under conditions of, 40g intermediate polymers is taken to be dissolved in the acetone soln of 150mL, are gradually heating to 85
DEG C, constant temperature flows back 30min in advance；Take 2g methylnadic anhydrides, two different phenylpropyl alcohol of 0.14g peroxidating and 0.02g antioxidants 2,5-
Ditert-butylhydro quinone (addition is respectively 5%, 0.35% and the 0.05% of polymer quality) is dissolved in 25mL acetone, point
It repeatedly adds in the intermediate polymer solution through flowing back in advance and is uniformly mixed, 110 DEG C of back flow reaction 10h can obtain thick production
Object；
(4) 30g crude products are dissolved in 150mL THF, then add in 500mL methanol-water solutions (V:V=2:1) it stirs
Precipitation process is carried out, gained filter cake is rinsed 2-3 times with deionized water after filtering, is subsequently placed in 55 DEG C of dryings in vacuum drying chamber
48h obtains pale brown color substance, as biology base epoxy hardener.
Infrared spectrum detection can determine that the structure of the curing agent prepared by the present embodiment is：
Biological based epoxy curing agent prepared by the present invention is brown color solid product, need before use by its
(80-90 DEG C) heating melting under certain temperature.
Acid value testing result to the curing agent prepared by the embodiment of the present invention 1~4 is 303-350mg KOH/g, is referred to
Dosage is 25~60phr (dosage of curing agent is 25~60g i.e. needed for 100g epoxy resin), and gel time is (i.e. in a constant temperature
To the time occurred used in solid gel after liquid resin is mixed with curing agent under degree)：45~50min at 80 DEG C, 30 at 90 DEG C
~36min.
Following experimental example 1~3 is by weighing a certain amount of epoxy resin E51 (South Asia), curing agent (molten state), accelerating agent
DMP-30 is uniformly mixed in reactor, stands whether a period of time observation resin solution is layered, and is finally infused resin into
Curing and rear curing process in the closing grinding tool that the pre-heat treatment is crossed, the performance for being cooled to room temperature test resin batten (the results are shown in Table
1)。
Experimental example 1
Curing agent -1 used in this experimental example is the curing agent prepared by embodiment 1；
Precise epoxy resin 80g, -1 30g of curing agent, altax P-30 0.5% heat (80- in beaker
90 DEG C) under the conditions of stir evenly, stand one section between observation resin solution whether be layered；It infuses resin at preheating in advance
Cure 4h for 90 DEG C in the closed grinding tool managed, cure 1h, the performance of last test resin batten after 110 DEG C；Experimental result is shown
Do not occur being layered inside resin batten or particulate matter precipitation phenomenon, show that compatibility is good；Curing degree is more than 95%.
Experimental example 2
Curing agent -2 used in this experimental example is the curing agent prepared by embodiment 2；
Precise epoxy resin 80g, -2 24g of curing agent, altax P-30 0.5% heat (80- in beaker
90 DEG C) under the conditions of stir evenly, stand a period of time observation resin solution whether be layered；It infuses resin at preheating in advance
Cure 4h for 90 DEG C in the closed grinding tool managed, cure 1h, the performance of last test resin batten after 110 DEG C；Experimental result is shown
Do not occur being layered inside resin batten or particulate matter precipitation phenomenon, show that compatibility is good；Curing degree is more than 95%.
Experimental example 3
Curing agent -3 used in this experimental example is the curing agent prepared by embodiment 3；
Precise epoxy resin 80g, -3 30g of curing agent, altax P-30 1% heat (80-90 in beaker
DEG C) under the conditions of stir evenly, stand one section between observation resin solution whether be layered；Infuse resin into the pre-heat treatment in advance
Cure 4h for 90 DEG C in the closed grinding tool crossed, cure 1h, the performance of last test resin batten after 110 DEG C；Experimental result display tree
Do not occur being layered inside fat batten or particulate matter precipitation phenomenon, show that compatibility is good；Curing degree is more than 95%.
Comparative example 1
Precise epoxy resin 80g, curing agent (maleic anhydride) 45g, accelerating agent 0.5% are in beaker, heating
It is stirred evenly under the conditions of (100-120 DEG C), whether observation resin solution is layered between standing one section；It infuses resin into advance
120 DEG C of curings 4h, 140 DEG C of curings 2 h, 160 DEG C of curing 2h in the closed grinding tool that the pre-heat treatment is crossed, last test resin batten
Performance；Curing degree is 90%.
Table 1：The performance parameter of epoxy resin batten prepared by experimental example 1~3, comparative example 1
Note：Tensile property and bending property are respectively according to resin cast in GB/T 1040-1992 and GB/T 2567-1995
Body performance test standard, using omnipotent mechanics machine (loading speed is respectively 1cm/min and 2 cm/min) (many will detectors
Device Co., Ltd) it is tested；The shock resistance test of resin uses XJU-5.5 anti-impacts according to ISO179-1-2010
Testing machine is hit to be tested；Dynamic thermomechanical analysis apparatus (heating rate is 2 DEG C/min) is used to measure the glass transition of resin
Temperature Tg.
It can be seen from the statistical data in table 1 present invention curing gained solidfied material curing degree can reach 95% with
On, the infared spectrum of the epoxy resin cured product prepared by experimental example 1 is as shown in Fig. 2, from the infrared of the upper epoxy monomer of figure
Spectrogram can see, 1603cm-1、1502cm-1And 910cm-1Characteristic absorption peak for epoxy monomer；Compared to asphalt mixtures modified by epoxy resin
Alicyclic monomer, using the obtained solidfied material (condition of cure of biology base curing agent solidification epoxy monomer：90℃/4h+110℃/
In 1603cm in spectrogram 1h)-1、1500cm-1And 906cm-1Nearby equally there is the characteristic absorption peak of epoxy monomer,
And 906cm-1The characteristic absorption peak of place's epoxy group is obviously reduced, and almost disappears, at the same time in 3447cm-1Near
There is the characteristic peak of OH, 2964cm-1And 1739cm-1Respectively CH3With the stretching vibration absworption peak of C=O, the feature of acid anhydrides is inhaled
Peak is received to disappear；It is possible thereby to infer that cross-linking reaction, epoxy group and curing has occurred with biology base curing agent in epoxy monomer
Active group such as COOH and acid anhydrides in agent have occurred ring-opening reaction and produce OH, and then have promoted curing reaction progress, i.e. ring
Oxygen resin solidification；This is mutually confirmed with measured epoxy resin cure degree.And use the resin-like prepared by Common curing agents
The curing degree of item is only 90%, hence it is evident that and less than the curing degree of resin batten in experimental example of the present invention, and hardening time is longer, Gu
It is higher to change temperature.
In addition, tensile strength, bending strength, elongation at break, the anti-impact of the resin batten of curing agent using the present invention
Hit intensity and glass transition temperature are all significantly better than the resin batten performance using Common curing agents.
Claims (1)
1. a kind of structural formula isCompound is consolidated as biological base epoxy
The purposes of agent, in the structural formula, m value ranges are the positive integer between 3~100, R1ForR2For。
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